Poly(ethylene glycol) (PEG)-based films, nanotubes, and nanotube arrays were successfully made using layer-by-layer (LbL) assembly ion-containing PEO derivatives on porous templates and planar substrates. PEG nanotubes are challenging to produce because PEG dissolves into solutions and solvents used during nanotube processing, but our techniques circumvent the issue. Nanotube dimensions were verified using microscopy and the average observed diameter was 155 nm. The PEG-based structures showed remarkable stability in water, salt water, and sodium hydroxide solution.